US4533774A - Process for the production of ethylene glycol - Google Patents

Process for the production of ethylene glycol Download PDF

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Publication number
US4533774A
US4533774A US06/554,846 US55484683A US4533774A US 4533774 A US4533774 A US 4533774A US 55484683 A US55484683 A US 55484683A US 4533774 A US4533774 A US 4533774A
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United States
Prior art keywords
weight
formaldehyde
amount
peroxide
ethylene glycol
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Expired - Fee Related
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US06/554,846
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English (en)
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Colin G. Griggs
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BP PLC
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BP PLC
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Assigned to BRITISH PETROLEUM COMPANY P.L.C., THE reassignment BRITISH PETROLEUM COMPANY P.L.C., THE ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: GRIGGS, COLIN G.
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/36—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal
    • C07C29/38—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal by reaction with aldehydes or ketones
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12C—BEER; PREPARATION OF BEER BY FERMENTATION; PREPARATION OF MALT FOR MAKING BEER; PREPARATION OF HOPS FOR MAKING BEER
    • C12C11/00—Fermentation processes for beer
    • C12C11/02—Pitching yeast

Definitions

  • the present invention relates to a process for the production of ethylene glycol.
  • Ethylene glycol is a very large tonnage industrial chemical which finds direct use in automotive coolant and antifreeze solutions, as a heat-transfer agent in refrigeration, and as an ingredient of deicing fluids for airport runways. Its uses as a chemical intermediate include its incorporation as an essential constituent in polyester fibres, films and bottle resins. It is also used as a solvent in for example lacquers, printing inks and adhesives.
  • ethylene glycol can be produced by reacting formaldehyde with carbon monoxide and water at high pressures (over 300 bars) in the presence of an acid catalyst to produce hydroxyacetic (glycollic) acid, reacting the acid so-produced with methanol to form the methyl ester and thereafter converting the methyl ester to ethylene glycol by catalytic hydrogenation.
  • Another process disclosed in U.S. Pat. Nos. 4,115,428 and 4,115,433, describes the production of ethylene glycol by reacting methanol and carbon monoxide at high pressures using a rhodium catalyst.
  • GB-A-2083038 discloses a process for producing ethylene glycol by reacting methanol, an organic peroxide, and formaldehyde in the presence of water (suitably from about 0.5 to about 35 weight percent), said organic peroxide having the formula R--O--O--R 1 wherein R and R 1 each is an alkyl or aralkyl group containing 3 to 12 carbon atoms, wherein no more than about 6 percent of organic peroxide, based on the total weight of methanol, organic peroxide, formaldehyde and water present, is utilised in the initial reaction mixture.
  • GB-A-2083037 describes a similar process in which a basic material is added to the reactants in an amount sufficient to reduce the hydrogen ions that are being formed in the reaction without unduly reducing the ethylene glycol production due to by-product formation.
  • the monomeric aqueous formaldehyde was produced from paraformaldehyde by adding a small amount of hydrogen chloride to depolymerise the paraformaldehyde to aqueous monomeric formaldehyde and thereafter the formaldehyde solution was neutralised by the addition of a small amount of sodium bicarbonate.
  • U.S. Pat. No. 4,393,252 discloses subject matter similar to that of GB-A-2083037.
  • EP-A-71457 discloses the improvement wherein the formaldehyde and the organic peroxide are added portionwise at intervals throughout the reaction period.
  • EP-A-71458 discloses the improvement wherein the amount of the peroxide used is greater than 6 and up to 25 weight percent and the amounts of water used is from 0.5 to 36 weight percent, and the amount of the peroxide and water used are dependent on each other so that either the amount of the peroxide used is greater than 6 up to 12 weight percent and the amount of water used is from 0.5 to 35 weight percent, or the amount of the peroxide used is greater than 12 up to 15 weight percent and the amount of water used is from 0.5 to 25 weight percent, or the amount of the peroxide used is greater than 15 up to 20 percent and the amount of water used is from 0.5 to 15 weight percent, or the amount of the peroxide used is greater than 20 to 25 weight percent and the amount of water used is from 0.5 to 10 weight percent, the above weight percentages being based on the total weight of the methanol, organic peroxide,
  • a polymeric source of formaldehyde can be employed without adding acid to depolymerise it to monomeric formaldehyde, thereby eliminating the acid neutralisation step.
  • using substantially anhydrous conditions and a polymeric source of formaldehyde better conversions to ethylene glycol can be achieved and in particular increased ratios of ethylene glycol to dialkyl peroxide can be obtained at low peroxide initiator levels.
  • the present invention provides a process for the production of ethylene glycol which process comprises reacting at elevated temperature methanol, a polymeric source of formaldehyde and an organic peroxide having the formula R--O--O--R 1 wherein R and R 1 are independently either alkyl or aralkyl groups containing from 3 to 12 carbon atoms.
  • Suitable polymeric sources of formaldehyde include paraformaldehyde, otherwise known as paraform, trioxane and tetraoxane, of which paraformaldehyde is preferred.
  • Paraformaldehyde is a solid mixture of linear poly(oxymethylene glycols) of relatively short chain length and may be represented by the formula HO(CH 2 O) n H, wherein n is 8-100.
  • Commercially available forms of paraformaldehyde generally have an average molecular weight of about 600 and may contain up to about 9 wt % water and a maximum acidity as formic acid of 0.03 wt %. Such commercially available forms may be used in the process of the present invention without further purification.
  • the commercially available forms may be further purified before use in the process.
  • higher molecular weight i.e. n greater than 100, suitably in the range from 100 to 500, forms of polyoxymethylene glycols of the formula HO(CH 2 O) n H may be employed.
  • Trioxane which may also be used in the process of the present invention is the cyclic symmetrical trimer of formaldehyde and is also a solid. Trioxane is also commercially available. Tetraoxane, which is a cyclic tetramer of formaldehyde, is a solid.
  • the organic peroxide having the formula R--O--O--R 1 wherein R and R 1 are independently either alkyl or aralkyl groups containing from 3 to 12 carbon atoms may suitably be di-tertiary-butyl peroxide, di-cumyl peroxide, tertiary-butyl cumyl peroxide or tertiary-butyl ethyl benzyl peroxide.
  • the peroxide is either di-cumyl peroxide or ditertiary-butyl peroxide.
  • a typical feed may comprise from about 45 to about 97% by weight, preferably from about 80 to about 90% by weight of methanol, from about 0.5 to about 50% by weight, preferably from about 2 to about 12% by weight of the polymeric source of formaldehyde, from about 0.25 to about 15% by weight, preferably from about 0.75 to about 3% by weight of organic peroxide and from about 0.5 to about 35% by weight of water, all percentages by weight being based on the total weight of the reactants.
  • the process may suitably be operated at a temperature greater than 100° C., for example in the range 100° to 200° C., preferably from 125° to 175° C. Under certain conditions, it may be desirable to operate at a temperature below 100° C.
  • the process may be operated at autogenous pressure, that is the pressure generated in a closed reactor at the particular reaction temperature though pressures above and below autogenous may be used if so desired.
  • the reaction time for a batch operation may suitably be in the range from 0.25 to 8 hours, preferably from 0.5 to 4 hours.
  • the process may be operated batchwise, semi-continuously or continuously, preferably continuously. Suitable methods of operation are described in the aforesaid EP-A-71457 and EP-A-71458, for example. Such methods include the portionwise addition of the organic peroxide and polymeric source of formaldehyde at intervals throughout the reaction period.
  • the product mixture may be purified using conventional techniques, such as distillation or solvent extraction, to recover ethylene glycol of the desired purity.
  • ethylene glycol there may also be formed by-products, such as t-butanol, methylal, methyl formate, glycerine and acetone. Since methylal is not an ethylene glycol precursor, its formation may lower the productivity of the process on a once-through basis.
  • Suitable basic materials are defined and exemplified in GB-A-2083037, to which the reader is hereby referred.
  • the paraformaldehyde as used in the Examples, was supplied by Fisons. It conforms with the formula HO(CH 2 O) n H wherein n is in the range from 8 to 100 and has an average value of about 60.
  • the water content of the paraformaldehyde is less than or equal to 2%, the formaldehyde content is about 97% and the rest is methanol.
  • Examples 1 to 6 The procedure of Examples 1 to 6 was repeated except that di-cumyl peroxide (DCP) was used in place of di-t-butylperoxide and that Examples 10, 12, 14 and 16 had reaction times of only one hour.
  • DCP di-cumyl peroxide
  • Table 3 The compositions etc are shown in Table 3. Noteworthy are the high EG/DCP ratios obtained at low peroxide level.
  • the Examples also illustrate the effect of reaction time, the reactions with DCP being faster than those with DTBP and largely complete after one hour.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Food Science & Technology (AREA)
  • Health & Medical Sciences (AREA)
  • Biochemistry (AREA)
  • Bioinformatics & Cheminformatics (AREA)
  • General Engineering & Computer Science (AREA)
  • General Health & Medical Sciences (AREA)
  • Genetics & Genomics (AREA)
  • Mycology (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Microbiology (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US06/554,846 1982-11-27 1983-11-23 Process for the production of ethylene glycol Expired - Fee Related US4533774A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB8233896 1982-11-27
GB8233896 1982-11-27

Publications (1)

Publication Number Publication Date
US4533774A true US4533774A (en) 1985-08-06

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US06/554,846 Expired - Fee Related US4533774A (en) 1982-11-27 1983-11-23 Process for the production of ethylene glycol

Country Status (10)

Country Link
US (1) US4533774A (de)
EP (1) EP0110666B1 (de)
JP (1) JPS59139331A (de)
AT (1) ATE29711T1 (de)
AU (1) AU565715B2 (de)
CA (1) CA1219603A (de)
DE (1) DE3373650D1 (de)
NO (1) NO157499C (de)
NZ (1) NZ206405A (de)
ZA (1) ZA838819B (de)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7301054B1 (en) 2006-09-29 2007-11-27 Eastman Chemical Company Process for the preparation of glycolaldehyde
US20080081931A1 (en) * 2006-09-29 2008-04-03 Eastman Chemical Company Process for the preparation of glycolaldehyde

Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2368494A (en) * 1940-12-28 1945-01-30 Standard Oil Dev Co Reactions of tertiary olefins with aldehydes
US2426017A (en) * 1943-10-08 1947-08-19 Du Pont Process for preparing 1,3-butylene glycol
GB625909A (en) * 1946-08-14 1949-07-06 Du Pont Manufacture of polyhydroxy compounds
US3081357A (en) * 1960-05-24 1963-03-12 Du Pont Process for producing alkanediols
US3414588A (en) * 1964-01-29 1968-12-03 Mobil Oil Corp Condensation of aldehydes with unsaturated compounds
US3438997A (en) * 1963-05-13 1969-04-15 Shell Oil Co Polyol synthesis using formaldehyde and olefins
US4144401A (en) * 1976-10-21 1979-03-13 Chevron Research Company Alcohol production
US4200765A (en) * 1976-09-17 1980-04-29 National Distillers And Chemical Corporation Glycol aldehyde and ethylene glycol processes
US4337371A (en) * 1980-09-02 1982-06-29 Celanese Corporation Production of ethylene glycol by reaction of methanol, an organic peroxide and formaldehyde
US4356332A (en) * 1981-10-29 1982-10-26 Texaco Inc. Process for preparing ethylene glycol
US4393252A (en) * 1981-07-28 1983-07-12 Redox Technologies, Inc. Process for producing ethylene glycol
US4412084A (en) * 1981-07-28 1983-10-25 John Kollar Process for producing ethylene glycol
US4412085A (en) * 1980-09-02 1983-10-25 John Kollar Process for producing ethylene glycol

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA1180353A (en) * 1980-09-02 1985-01-02 John Kollar Process for producing ethylene glycol
US4345104A (en) * 1981-06-30 1982-08-17 Union Carbide Corporation Process for the production of ethylene glycol

Patent Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2368494A (en) * 1940-12-28 1945-01-30 Standard Oil Dev Co Reactions of tertiary olefins with aldehydes
US2426017A (en) * 1943-10-08 1947-08-19 Du Pont Process for preparing 1,3-butylene glycol
GB625909A (en) * 1946-08-14 1949-07-06 Du Pont Manufacture of polyhydroxy compounds
US3081357A (en) * 1960-05-24 1963-03-12 Du Pont Process for producing alkanediols
US3438997A (en) * 1963-05-13 1969-04-15 Shell Oil Co Polyol synthesis using formaldehyde and olefins
US3414588A (en) * 1964-01-29 1968-12-03 Mobil Oil Corp Condensation of aldehydes with unsaturated compounds
US4200765A (en) * 1976-09-17 1980-04-29 National Distillers And Chemical Corporation Glycol aldehyde and ethylene glycol processes
US4144401A (en) * 1976-10-21 1979-03-13 Chevron Research Company Alcohol production
US4337371A (en) * 1980-09-02 1982-06-29 Celanese Corporation Production of ethylene glycol by reaction of methanol, an organic peroxide and formaldehyde
US4412085A (en) * 1980-09-02 1983-10-25 John Kollar Process for producing ethylene glycol
US4393252A (en) * 1981-07-28 1983-07-12 Redox Technologies, Inc. Process for producing ethylene glycol
US4412084A (en) * 1981-07-28 1983-10-25 John Kollar Process for producing ethylene glycol
US4356332A (en) * 1981-10-29 1982-10-26 Texaco Inc. Process for preparing ethylene glycol

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7301054B1 (en) 2006-09-29 2007-11-27 Eastman Chemical Company Process for the preparation of glycolaldehyde
US20080081931A1 (en) * 2006-09-29 2008-04-03 Eastman Chemical Company Process for the preparation of glycolaldehyde
US20080081759A1 (en) * 2006-09-29 2008-04-03 Eastman Chemical Company Process for the preparation of glycolaldehyde
US7420093B2 (en) 2006-09-29 2008-09-02 Eastman Chemical Company Process for the preparation of glycolaldehyde

Also Published As

Publication number Publication date
NO157499B (no) 1987-12-21
JPS59139331A (ja) 1984-08-10
ZA838819B (en) 1985-07-31
EP0110666B1 (de) 1987-09-16
CA1219603A (en) 1987-03-24
AU2170883A (en) 1984-05-31
ATE29711T1 (de) 1987-10-15
AU565715B2 (en) 1987-09-24
EP0110666A2 (de) 1984-06-13
NO157499C (no) 1988-03-30
NO834350L (no) 1984-05-28
DE3373650D1 (en) 1987-10-22
EP0110666A3 (en) 1986-03-19
NZ206405A (en) 1985-10-11

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Owner name: BRITISH PETROLEUM COMPANY P.L.C., THE BRITANNIC HO

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Effective date: 19831117

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Effective date: 19930808

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Free format text: PATENT EXPIRED DUE TO NONPAYMENT OF MAINTENANCE FEES UNDER 37 CFR 1.362